EP2384325B1 - Process for preparing divinylarene dioxides - Google Patents
Process for preparing divinylarene dioxides Download PDFInfo
- Publication number
- EP2384325B1 EP2384325B1 EP09760062.1A EP09760062A EP2384325B1 EP 2384325 B1 EP2384325 B1 EP 2384325B1 EP 09760062 A EP09760062 A EP 09760062A EP 2384325 B1 EP2384325 B1 EP 2384325B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- divinylarene
- alkyl
- aryl
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 86
- 238000000034 method Methods 0.000 claims description 54
- 230000008569 process Effects 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 47
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 46
- YDIZFUMZDHUHSH-UHFFFAOYSA-N 1,7-bis(ethenyl)-3,8-dioxatricyclo[5.1.0.02,4]oct-5-ene Chemical compound C12OC2C=CC2(C=C)C1(C=C)O2 YDIZFUMZDHUHSH-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 34
- 239000003607 modifier Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 15
- -1 manganese salen complexes Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000007527 lewis bases Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229960003540 oxyquinoline Drugs 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 claims 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical group CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 239000000412 dendrimer Substances 0.000 claims 1
- 229920000736 dendritic polymer Polymers 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- KAHROKHAOQFUTL-UHFFFAOYSA-N gold(3+) oxygen(2-) titanium(4+) Chemical group [O--].[O--].[Ti+4].[Au+3] KAHROKHAOQFUTL-UHFFFAOYSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 229920000223 polyglycerol Polymers 0.000 claims 1
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 10
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 9
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000006735 epoxidation reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 150000002118 epoxides Chemical group 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 3
- 241001120493 Arene Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RHLWQEFHFQTKNT-UHFFFAOYSA-N (2z)-1-cyclooctyl-2-diazocyclooctane Chemical compound [N-]=[N+]=C1CCCCCCC1C1CCCCCCC1 RHLWQEFHFQTKNT-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- ILSRXKFYTXYKJS-UHFFFAOYSA-N 2,4-bis(ethenyl)-3,6-dioxatetracyclo[6.4.0.02,4.05,7]dodeca-1(12),8,10-triene Chemical compound C=CC12OC1(C=C)C1=CC=CC=C1C1C2O1 ILSRXKFYTXYKJS-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- GLPDXGJXUWGMQJ-UHFFFAOYSA-N 4-ethenyl-7-(4-ethenylphenyl)-3,8-dioxatricyclo[5.1.0.02,4]oct-5-ene Chemical compound C(=C)C1=CC=C(C=C1)C12C(C3C(C=C1)(C=C)O3)O2 GLPDXGJXUWGMQJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical class [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 2
- TWIIVLKQFJBFPW-UHFFFAOYSA-N acetaminosalol Chemical compound C1=CC(NC(=O)C)=CC=C1OC(=O)C1=CC=CC=C1O TWIIVLKQFJBFPW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003592 biomimetic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- MTCBLMPRPUTXHZ-UHFFFAOYSA-N n-(oxomethylidene)nitramide Chemical compound [O-][N+](=O)N=C=O MTCBLMPRPUTXHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- AUTBTTGBSQUMMR-UHFFFAOYSA-N 1,6-bis(ethenyl)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C=C)C1(C=C)O2 AUTBTTGBSQUMMR-UHFFFAOYSA-N 0.000 description 1
- LZUMVTPOQOUWRQ-UHFFFAOYSA-N 1-(2-aminohydrazinyl)hexane Chemical compound CCCCCCNNN LZUMVTPOQOUWRQ-UHFFFAOYSA-N 0.000 description 1
- UZXQULFXZDNGSO-UHFFFAOYSA-N 1-but-1-enyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C=CCC)C1O2 UZXQULFXZDNGSO-UHFFFAOYSA-N 0.000 description 1
- WISUILQECWFZCN-UHFFFAOYSA-N 2-(oxiran-2-ylmethylsulfanylmethyl)oxirane Chemical compound C1OC1CSCC1CO1 WISUILQECWFZCN-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 150000004325 8-hydroxyquinolines Chemical class 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Natural products C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- QIFOFCWBJPAXTM-UHFFFAOYSA-N chembl375232 Chemical compound C1=CC(C(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CN=CC=1)=C1C=CC(=N1)C(C=1C=CN=CC=1)=C1C=CC(N1)=C1C=2C=CN=CC=2)=C2N=C1C=C2 QIFOFCWBJPAXTM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- SGKRJERPWBDBKS-UHFFFAOYSA-K iron(3+);pyridine-2,6-dicarboxylic acid;trichloride Chemical compound Cl[Fe](Cl)Cl.OC(=O)C1=CC=CC(C(O)=O)=N1 SGKRJERPWBDBKS-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VUPVVQPVTXZTAW-UHFFFAOYSA-N manganese(3+) quinolin-8-ol Chemical compound [Mn+3].C1=CN=C2C(O)=CC=CC2=C1 VUPVVQPVTXZTAW-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- MTYUUSLAONENAZ-UHFFFAOYSA-N n,n-dioctylnonan-2-amine;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCN(CCCCCCCC)C(C)CCCCCCC MTYUUSLAONENAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- FNXKBSAUKFCXIK-UHFFFAOYSA-M sodium;hydrogen carbonate;8-hydroxy-7-iodoquinoline-5-sulfonic acid Chemical class [Na+].OC([O-])=O.C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 FNXKBSAUKFCXIK-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ANRASKQFUDPONQ-UHFFFAOYSA-M tributyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC ANRASKQFUDPONQ-UHFFFAOYSA-M 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
Definitions
- the present invention is related to a process for preparing divinylarene dioxides, particularly those derived from divinylbenzene.
- Divinylarene dioxides. particularly divinylbenzene dioxide (DVBDO) and others which are derived from divinylarenes, particularly divinylbenzene (DVB), are a class of diepoxides which can be used as either reactive diluents or the main epoxy resin matrix in epoxy thermoset formulations.
- DVBDO itself has a very low liquid viscosity (for example less than about 20 mPa-s) making DVBDO especially useful in the preparation of low viscosity epoxy formulations.
- the epoxy formulations made from DVBDO are useful as intermediates in the production of various other products for example suitable for use in the fields of coatings, composites, and molding compositions.
- WO 9620233 discloses the preparation of epoxy-containing compounds by: (1) providing an allyl reagent; (2) allylating one or more compounds containing at least one active-hydrogen atom per molecule using the allyl reagent from step (1), whereby an allyl ether, allyl amine or allyl thioether compound is formed; and (3) converting the allyl groups on the compound from step (2) to epoxide groups, whereby a glycidyl ether, glycidyl amine or glycidyl thioether compound is formed, characterized in that the allyl reagent is an allyl carboxylate or allyl carbonate.
- the epoxy-containing compounds are useful in coatings, castings and laminates.
- the present invention is directed to a process for the preparation of divinylarene dioxides comprising:
- the process is carried out under conditions such that the co-production of undesirable by-products is minimized or is essentially eliminated.
- the process of the present invention also advantageously produces divinylarene dioxides in high yields, for example, in yields of greater than about 30 %.
- a catalyzed epoxidation of a divinylarene with hydrogen peroxide as the oxidizing agent in the presence of a catalyst and an organic modifier is carried out to form, for example, a divinylarene dioxide such as divinylbenzene dioxide; wherein the hydrogen peroxide is present in the reaction mixture in mole ratio per mole of divinylarene of at least 2 or more.
- a divinylbenzene may be dissolved in a solvent such as dichloromethane, and using hydrogen peroxide as the oxidizing agent, a catalyst, for example methyltrioxorhenium (MTO) and an organic modifier such as 3-methyl pyrazole (3MP), are added to the reaction mixture; and then the reaction may be carried out at a temperature of between about 0 °C to about 100 °C.
- a catalyst for example methyltrioxorhenium (MTO) and an organic modifier such as 3-methyl pyrazole (3MP)
- the present invention comprises a process for preparing a divinylarene dioxide.
- a divinylarene dioxide of the present invention is prepared by reacting a divinylarene with hydrogen peroxide in the presence of an organic modifier and in the presence of a catalyst.
- a divinylarene dioxide such as divinylbenzene dioxide (DVBDO) is prepared by dissolving a divinylbenzene (DVB) in dichloromethane, using hydrogen peroxide (H 2 O 2 ) as the oxidizing agent.
- a catalyst for example methyltrioxorhenium (MTO) and an organic modifier such as 3-methyl pyrazole (3MP), are added to the reaction mixture; and then the reaction may be carried out at a temperature of between about 0 °C to about 100 °C. After the epoxidation is completed the solvent and organic modifier may be removed, and if desired, the product may be purified by known means such as distillation.
- MTO methyltrioxorhenium
- 3MP 3-methyl pyrazole
- the source of divinylarenes may come from processes which prepare divinylarenes such as for example; divinylarenes can be prepared with salt or metal wastes from arenes and ethylene.
- the divinylarene may consist of any substituted or unsubstituted arene nucleus bearing two vinyl groups in any ring position.
- the arene may include for example benzene, substituted benzenes, or (substituted) ring-annulated benzenes, and mixtures thereof.
- divinylbenzene may be ortho , meta , or para isomers or any mixture thereof.
- Additional substituents may consist of H 2 O 2 -resistant groups including for example saturated alkyl, aryl, halogen, nitro, isocyanate, or RO-(where R may be saturated alkyl or aryl), or mixtures thereof.
- Ring-annulated benzenes may include for example naphthlalene, tetrahydronaphthalene, and mixtures thereof.
- the divinylarene may contain quantities (such as for example less than about 20 weight percent) of substituted arenes.
- the amount and structure of the substituted arenes depend on the process used in the preparation of the divinylarene.
- DVB prepared by the dehydrogenation of diethylbenzene (DEB) may contain quantities of ethylvinylbenzene (EVB) and DEB.
- EVB ethylvinylbenzene
- DEB ethylvinylbenzene
- EVB ethylvinylbenzene monoxide while DEB remains unchanged.
- the divinylarene used in the process of the present invention may include for example divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide; and mixtures thereof.
- the concentration of the divinylarene used in the present invention may range generally from about 1 weight percent (wt%) to about 100 wt%, preferably from about 2 wt% to about 98 wt%, and more preferably from about 5 wt% to about 95 wt%.
- the oxidizing agent used in the process of the present invention is hydrogen peroxide.
- Hydrogen peroxide may be pre-manufactured or generated in-situ in the course of the reaction with the divinylarene, for example as disclosed in Edwards et al., J. Mater. Res., 22, (4) 831, 2007 ; or Hayashi et al., J. Catal., 178, 566, 1998 .
- Hydrogen peroxide may also be pre-manufactured using the anthraquinone/tetrahydroanthtraquinone process with an appropriate hydrogenation catalyst such as palladium on alumina or Raney nickel such as described in U.S. Patent No. 3,635,841 .
- the concentration of the H 2 O 2 oxidant used in the present invention may range generally from about 0.1 wt% to about 100 wt%, preferably from about 1 wt% to about 80 wt%, and more preferably from about 10 wt% to about 60 wt%.
- an optional solvent may be used in the process of the present invention.
- the optional solvent useful in the process of the present invention may include for example any inert organic solvent that is inert to H 2 O 2 under the reaction conditions.
- the solvent may include halogenated alkanes such as dichloromethane; aromatics such as toluene; polar organic solvents such as dimethyl formamide, or ethers such as tetrahydrofuran; alcohols such as t-amyl alcohol and methanol; or fluorinated alcohols such as trifluoroethanol; or mixtures thereof.
- the concentration of the solvent used in the present invention may be in the range of generally from about 1 wt% to about 99 wt%, preferably from about 5 wt% to about 95 wt%, and more preferably from about 10 wt% to about 90 wt%.
- the catalyst useful in the process of the present invention may include for example metal oxides such as alkyltrioxorhenium compounds; heteropolyacids such as phosphotungstate compounds; macroporous and mesomorphous zeolites such as titanium silicate compounds; and transition metal complexes of porphrins, phthalocyanines, and Schiff bases, pyridine and ring annulated pyridine derivatives with at least one or more additional coordinating groups; cyclam; cylen; 8-hydroxyquinoline derivatives; and mixtures thereof, wherein the transition metal may be include for example iron, cobalt, manganese.
- metal oxides such as alkyltrioxorhenium compounds
- heteropolyacids such as phosphotungstate compounds
- macroporous and mesomorphous zeolites such as titanium silicate compounds
- transition metal complexes of porphrins, phthalocyanines, and Schiff bases pyridine and ring annulated pyridine derivatives with at least one or more additional
- the catalyst of the present invention is methyltrioxorhenium.
- the catalyst of the present invention is in-situ generated or isolated ammonium salts of peroxophosphotungstic acid.
- These salts can be prepared from tungstic acid or phosphotungstic acid and hydrogen peroxide and ammonium salts.
- the ammonium salts are detailed below under other/optional components.
- the catalyst of the present invention may be selected from one or more titanium silicate compounds such as TS-1, MCM-41, ZSM-5 or SBA-1.
- titanium silicate compounds such as TS-1, MCM-41, ZSM-5 or SBA-1.
- Different transition metals such as Ti, V, Fe, Pd, Nb, Mn, Mo and Cr could be built into the silica frame work to reduce side reactions.
- the catalyst of the present invention is a transition metal complex.
- the transition metal for the catalyst is selected from the group comprising of iron, manganese, cobalt, vanadium, chromium, copper and mixtures thereof.
- the chelants may be cyclen, triazanonane, cyclam or their N-alkyl substituted derivatives.
- the chelants also may be Schiff bases originating from salicylic aldehyde (or alkyl, aryl substituted analogs) and diamines such as ethylene diamine, o-phenylene diamine, 1, 2-cyclohexyl diamine.
- Other variants for chelants are phtalocyanine or porphirin and their halogen and alkyl or aryl substituted analogs.
- the chelants could also be pyridine and ring annulated pyridine derivatives with at least one or more additional coordinating groups on any of the rings.
- the coordinating groups are selected from hydroxyl groups, thiols, carboxylic acid groups or iminium group in which the carbon can be substituted with alkyl, aryl, O-alkyl, O-aryl, N-alkyl, N-aryl, S-alkyl, or S-aryl groups and imine nitrogen can be substituted with alkyl or aryl groups.
- R 1 are carboxylic acid groups
- R 2 and R 3 could be alkyl, aryl, or O-alkyl, O-aryl, N-alkyl, N-aryl, S-alky or S-aryl groups and R 2 and R 3 could also be part of a ring system.
- R4 is situated at any ring position of the annulated ring system and selected from halogens, hydroxyl, thiol, alkyl or aryl groups.
- Preferred transition metal complex catalysts of the present invention are iron(III) chloride- 2,6-pyridine dicarboxylic acid complex modified with either diisopropylamine or benzylamine and manganese(III) 8-hydroxyquinoline complex and its 5,7-substituted analogs; and mixtures thereof.
- transition metal complexes of porphrins, phthalocyanines, and Schiff bases pyridine carboxylates, 8-hydroxy-quinoline, cyclam, cylen, N, N',N"-triazacyclononane which have been used for the epoxidation of styrene and its derivatives as disclosed in Shrinivas et al., Biomimetic Oxidations Using Transition Metal Complexes Encapsulated in Zeolites, Catalysis Surveys from Asia, vol 7, 2-3, 121-131, 2003 .
- the catalysts described in the above reference may be useful for the epoxidation of DVB and result in high yields and epoxide selectivity.
- catalysts described in the art include a rhenium based catalyst as disclosed in S. Yamakazi, Org. Biomol. Chem., 2007, 5, 2109 ; an Fe complex catalyst as disclosed in Anilkumar et al., An Efficient Biomimetic Fe-catalyzed Epoxidation of Olefins Using Hydrogen Peroxide, Chem.
- the concentration of the catalyst used in the present invention may range generally from about 0.001 wt% to about 5 wt%, preferably from about 0.01 wt% to about 1 wt%, and more preferably from about .0.1 wt% to about 0.5 wt%.
- the organic modifier used in the process of the present invention may include for example Lewis bases such as N-containing compounds; either alicyclic amines such as triethyl amine, ethylene diamine, benzyl amine or diisopropyl amine, or heterocyclic amines like pyrazole, pyridine, bipyridine, N,N-dimethylaminopyridine, diazobicyclooctane (DABCO) and their derivatives; N-oxides, alkyl or cyano-substituted analogs; and mixtures thereof.
- Lewis bases such as N-containing compounds
- alicyclic amines such as triethyl amine, ethylene diamine, benzyl amine or diisopropyl amine
- heterocyclic amines like pyrazole, pyridine, bipyridine, N,N-dimethylaminopyridine, diazobicyclooctane (DABCO) and their derivatives
- the organic modifier may depend on the catalyst used in the process of the present invention.
- the organic modifier may include a tertiary amine such as a pyridine or a pyrazole.
- the amines may be alkyl or aryl substituted at any ring position.
- the organic modifier may be a tertiary amine, ammonium salt, or a quaternary ammonium salt such as methyl-trioctylamine hydrogen sulfate, ammonium salts containing methyl or benzyl groups and long aliphatic hydrocarbon chains (C 10 -C 18 ), tricaprylammonium chloride, tributylhexadecylammonium bromide, benzalkonium chloride; and mixtures thereof.
- a tertiary amine, ammonium salt, or a quaternary ammonium salt such as methyl-trioctylamine hydrogen sulfate, ammonium salts containing methyl or benzyl groups and long aliphatic hydrocarbon chains (C 10 -C 18 ), tricaprylammonium chloride, tributylhexadecylammonium bromide, benzalkonium chloride; and mixtures thereof.
- the organic modifier may be a carboxylic acid, an ammonium carboxylate, or a carboxylic acid anhydride; and mixtures thereof.
- the organic modifier may be for example an aliphatic amine or an imidazole.
- N-heterocycles can be used for example pyrazole and pyrrolidine or carboxylate salts such as ammonium acetate or acetic acid; and mixtures thereof.
- the concentration of the organic modifier used in the present invention may range generally from about 0.01 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, and more preferably from about 1 wt% to about 10 wt%.
- the organic modifier may be added to the composition of the present invention to assist in the reaction process; and subsequently, the organic modifier may be removed, if desired, after its use.
- the resulting divinylarene dioxide reaction product is isolated and the concentration of the organic modifier in the reaction product is reduced to about 5 weight percent or less; and preferably the concentration of the organic modifier is reduced to about 0.5 weight percent or less.
- the concentration of the organic modifier is from about 0.004 weight percent to about 5 weight percent; more preferably the concentration of the organic modifier is from about 0.01 weight percent to about 5 weight percent; and most preferably the concentration of the organic modifier is from about 0.5 weight percent to about 1.5 weight percent.
- composition of the present invention including for example, other resins, stabilizers, fillers, plasticizers, catalyst de-activators; and mixtures thereof.
- the concentration of the optional additives used in the present invention may range generally from 0 wt% to about 99.9 wt%, preferably from about 0.1 wt% to about 99.9 wt%, more preferably from about 1 wt% to about 99 wt%, and most preferably from about 2 wt% to about 98 wt%. In another embodiment the additives may be from about 0.01 wt % to about 99.9 wt %.
- the preparation of divinylarene dioxides using H 2 O 2 without co-production of undesirable by-products may be achieved by (i) adding to a reactor the following reactants: a divinylarene, a catalyst, an organic modifier, and optionally an inert organic solvent; (ii) contacting the reactants with H 2 O 2 ; and then allowing the reactant components to react under reaction conditions to produce the corresponding divinylarene dioxide.
- the reaction of the divinylarene with the H 2 O 2 is carried out with an excess of or an equivalent moles of H 2 O 2 .
- the reaction is carried out at a H 2 O 2 :divinylarene mole ratio of at least 2 or more; preferably, from about 2 to about 50; more preferably, from about 2 to about 10; and most preferably, from about 2 to about 4 mole ratio. If less than two moles of H 2 O 2 per mole of divinylarene is used, there would not be sufficient amount of oxidizing agent to epoxidize both of the double bonds in the divinylarene. For example, using one mol H 2 O 2 could provide a product that contains one epoxide group and one double bond on average.
- the resulting reaction product may be unstable, i.e., the product may have an increase in viscosity, and ultimately may gel prior to reaction with an epoxy curing agent. If above 50 moles of H 2 O 2 per mole of divinylarene is used, the benefits of using the H 2 O 2 oxidant in the reaction may no longer be economical; and use of more H 2 O 2 oxidant may be wasteful.
- the reaction conditions include carrying out the reaction under a temperature, generally in the range of from about 0 °C to about 100 °C, preferably from about 5°C to about 80°C, and more preferably from about 20 °C to about 60 °C.
- the pressure of the reaction may be generally from about 0.1 atmosphere (atm) to about 10 atm.
- the reaction process of the present invention may be a batch or a continuous process.
- the reactor used in the process may be any reactor and ancillary equipment well known to those skilled in the art.
- the insubstantial quantities of the undesirable by-products produced in the reaction of the present invention are generally, less than about 20 wt % of undesirable by-products; preferably, less than about 10 wt %,; more preferably, less than about 5 wt %; and most preferably zero wt % undesirable by-products.
- the co-produced water; and any remaining organic modifier, catalyst, and solvent may be removed to recover a usable divinylarene dioxide product.
- the product may optionally be purified by well-known means in the art such as by distillation, crystallization.
- One advantage of the present invention process is that high yields of divinylarene dioxides may be produced by the process of the present invention. With high yields of divinylarene dioxides produced, the process of the present invention advantageously requires less recycle and produces less waste.
- the "high yield" of the divinylarene dioxides produced by the process of the present invention is generally greater than about 30 %; and preferably, ranges from about 70 % to about 100 %; more preferably, from about 80 % to about 100 %; and most preferably, from about 90 % to about 100 % based on divinylarene starting material.
- the divinylarene dioxides prepared by the process of the present invention are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity than conventional epoxy resins.
- the divinylarene dioxide prepared by the process of the present invention may comprise, for example, any substituted or unsubstituted arene nucleus bearing two vinyl oxide(epoxide) groups in any ring position.
- the arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, or (substituted) ring-annulated benzenes or homologously bonded (substituted) benzenes, or mixtures thereof.
- the divinylbenzene portion of the divinylarene dioxide may be ortho , meta, or para isomers or any mixture thereof.
- Additional substituents may consist of H 2 O 2 -resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or RO- (where R may be a saturated alkyl or aryl).
- Ring-annulated benzenes may consist of naphthlalene, tetrahydronaphthalene.
- Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether.
- the divinylarene oxide product prepared by the process of the present invention may be illustrated generally by general chemical Structures I -IV as follows:
- each R 1 , R 2 , R 3 and R 4 individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a H 2 O 2 -resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; and z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.
- the divinylarene dioxide product produced by the process of the present invention may include for example alkyl-vinyl-arene monoxides depending on the presence of alkylvinylarene in the starting material.
- the divinylarene dioxide produced by the process of the present invention may include for example divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.
- the present invention includes a DVBDO illustrated by any one of the above Structures individually or as a mixture thereof.
- Structures V and VI above show the meta (1, 3-DVBDO) and para (1,4-DVDBO) isomers of DVBDO, respectively.
- the ortho isomer is rare; and usually a mixture of DVBDO is mostly produced as an about 2:1 ratio of meta (Structure V) to para (Structure VI).
- the present invention preferably includes as one embodiment an about 2:1 ratio of Structure V to Structure VI.
- the process of the present invention is particularly suited for the preparation of divinylbenzene dioxide, a low viscosity liquid epoxy resin.
- the viscosity of the divinylarene dioxides produced by the process of the present invention ranges generally from about 10 mPa-s to about 100 mPa-s; preferably, from about 10 mPa-s to about 50 mPa-s; and more preferably, from about 10 mPa-s to about 25 mPa-s at 25 °C.
- the utility of the divinylarene dioxides of the present invention requires their thermal stability to allow their formulation or processing at moderate temperatures (for example, at from about 100 °C to about 200 °C) for up to several hours (for example, for at least 2 hours) without oligomerization or homopolymerization. Oligomerization or homopolymerization during formulation or processing is evident by a substantial increase in viscosity or gelling (crosslinking).
- the divinylarene dioxides of the present invention have sufficient thermal stability such that they do not experience a substantial increase in viscosity or gelling during formulation or processing at moderate temperatures.
- Phosphotungstic acid H 3 ⁇ PO 4 (WO 3 ) 12 ⁇ , 0.1 g, 0.03 mmol
- water 1 mL
- Phosphoric acid (30%, 0.022 g, 0.07 mmol) was added, followed by H 2 O 2 (29%, 0.102 g 0.9 mmol).
- the reaction mixture was stirred at 20 °C for 30 minutes when Aliquat 336 (0.126 g, 0.3 mmol) was added in dichloroethane solution (5 mL).
- the reaction mixture was stirred at 20 °C for 20 minutes.
- FeCl 3 hexahydrate (0.025 mmol) and 2,6-pyridine dicarboxylic acid (0.025 mmol) were mixed in t -amyl alcohol (9 mL) in each of four 20 mL vials equipped with a magnetic stirbar. After stirring 15 minutes, diisopropylamine (3.5 ⁇ L, 7.0 ⁇ L and 10.5 ⁇ L; 0.025, 0.05 and 0.75 mmol, respectively) were added to three separate vials. One vial had no additional amine added to act as a control. To each of the four vials was also added dodecane (57 ⁇ L, 0.25 mmol) as an internal standard. The resulting solutions were allowed to stir an additional 30 minutes.
- Mn(III) complexes were prepared by a literature procedure described in ( J. of Catalysis, 256, 154, 2008 ). A general procedure for testing the manganese(III) complexes of HQ and its halogen substituted analogs is given here.
- DVB (1 mmol, 80 % DVB, 20 % EVB), catalyst (0.04 mmol), additives, and acetone (3 mL) were transferred into a vial.
- Ammonium acetate (0.1 mmol) and glacial acetic acid (0.2 mmol) either together or separately were used as additives.
- hydrogen peroxide (30%, 3 mmol) was added in 5 aliquots in the course of 15 minutes.
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Description
- The present invention is related to a process for preparing divinylarene dioxides, particularly those derived from divinylbenzene.
- Divinylarene dioxides. particularly divinylbenzene dioxide (DVBDO) and others which are derived from divinylarenes, particularly divinylbenzene (DVB), are a class of diepoxides which can be used as either reactive diluents or the main epoxy resin matrix in epoxy thermoset formulations. DVBDO itself has a very low liquid viscosity (for example less than about 20 mPa-s) making DVBDO especially useful in the preparation of low viscosity epoxy formulations. The epoxy formulations made from DVBDO are useful as intermediates in the production of various other products for example suitable for use in the fields of coatings, composites, and molding compositions.
- There are previously known processes for the preparation of DVBDO using hydrogen peroxide (H2O2). However, none of these previously known prior art processes can produce DVBDO in high yields efficiently and economically. For example, the process described in Inoue et al, Bull. Chem. Soc. Jap., 1991, 64, 3442, employs a molybdenum catalyst and sodium nitrate or sodium sulfate additives providing yields of DVBDO at less than 10 % because of product instability and catalyst deactivation.
JP 09286750 -
WO 9620233 - The above processes known in the prior art have not successfully provided DVBDO in high yields (for example greater than 30 %). In addition, the prior art processes do not produce DVBDO without co-production of undesirable by-products such as acetamide or acetic acid.
- It is therefore desired to provide a process for preparing divinylarene dioxides, particularly those derived from divinylbenzene, using H2O2 without co-production of undesirable by-products; and wherein the divinylarene dioxide is produced in high yields using an economical and efficient process.
- The present invention is directed to a process for the preparation of divinylarene dioxides comprising:
- a) reacting a divinylarene with hydrogen peroxide as the oxidizing agent in the presence of a catalyst and an organic modifier to form a divinylarene dioxide; wherein the hydrogen peroxide is present in an excess or an equivalent mole ratio per mole of vinyl group; wherein said organic modifier is a Lewis base, and wherein said divinylarene dioxide is produced at at a yield of greater than 30 %; and
- b) isolating the divinylarene dioxide reaction product; and reducing the concentration of said organic modifier in the reaction product to 5 weight percent or less.
- The process is carried out under conditions such that the co-production of undesirable by-products is minimized or is essentially eliminated. The process of the present invention also advantageously produces divinylarene dioxides in high yields, for example, in yields of greater than about 30 %.
- In one embodiment of the present invention, a catalyzed epoxidation of a divinylarene with hydrogen peroxide as the oxidizing agent in the presence of a catalyst and an organic modifier is carried out to form, for example, a divinylarene dioxide such as divinylbenzene dioxide; wherein the hydrogen peroxide is present in the reaction mixture in mole ratio per mole of divinylarene of at least 2 or more.
- As an illustration of the present invention, a divinylbenzene may be dissolved in a solvent such as dichloromethane, and using hydrogen peroxide as the oxidizing agent, a catalyst, for example methyltrioxorhenium (MTO) and an organic modifier such as 3-methyl pyrazole (3MP), are added to the reaction mixture; and then the reaction may be carried out at a temperature of between about 0 °C to about 100 °C.
- The present invention is not limited to the specific embodiments described below, but rather; the present invention includes all alternatives, modifications, and equivalents falling within the true scope of the appended claims.
- In its broadest scope, the present invention comprises a process for preparing a divinylarene dioxide. A divinylarene dioxide of the present invention is prepared by reacting a divinylarene with hydrogen peroxide in the presence of an organic modifier and in the presence of a catalyst. For example, in one embodiment, a divinylarene dioxide such as divinylbenzene dioxide (DVBDO) is prepared by dissolving a divinylbenzene (DVB) in dichloromethane, using hydrogen peroxide (H2O2) as the oxidizing agent. A catalyst, for example methyltrioxorhenium (MTO) and an organic modifier such as 3-methyl pyrazole (3MP), are added to the reaction mixture; and then the reaction may be carried out at a temperature of between about 0 °C to about 100 °C. After the epoxidation is completed the solvent and
organic modifier may be removed, and if desired, the product may be purified by known means such as distillation. - In one embodiment, the source of divinylarenes may come from processes which prepare divinylarenes such as for example; divinylarenes can be prepared with salt or metal wastes from arenes and ethylene.
- In another embodiment, the divinylarene may consist of any substituted or unsubstituted arene nucleus bearing two vinyl groups in any ring position. The arene may include for example benzene, substituted benzenes, or (substituted) ring-annulated benzenes, and mixtures thereof. In one embodiment, divinylbenzene may be ortho, meta, or para isomers or any mixture thereof. Additional substituents may consist of H2O2-resistant groups including for example saturated alkyl, aryl, halogen, nitro, isocyanate, or RO-(where R may be saturated alkyl or aryl), or mixtures thereof. Ring-annulated benzenes may include for example naphthlalene, tetrahydronaphthalene, and mixtures thereof.
- In yet another embodiment, the divinylarene may contain quantities (such as for example less than about 20 weight percent) of substituted arenes. The amount and structure of the substituted arenes depend on the process used in the preparation of the divinylarene. For example, DVB prepared by the dehydrogenation of diethylbenzene (DEB) may contain quantities of ethylvinylbenzene (EVB) and DEB. Upon reaction with hydrogen peroxide, EVB produces ethylvinylbenzene monoxide while DEB remains unchanged.
- The divinylarene used in the process of the present invention may include for example divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide; and mixtures thereof.
- The concentration of the divinylarene used in the present invention may range generally from about 1 weight percent (wt%) to about 100 wt%, preferably from about 2 wt% to about 98 wt%, and more preferably from about 5 wt% to about 95 wt%.
- The oxidizing agent used in the process of the present invention is hydrogen peroxide. Hydrogen peroxide may be pre-manufactured or generated in-situ in the course of the reaction with the divinylarene, for example as disclosed in Edwards et al., J. Mater. Res., 22, (4) 831, 2007; or Hayashi et al., J. Catal., 178, 566, 1998. Hydrogen peroxide may also be pre-manufactured using the anthraquinone/tetrahydroanthtraquinone process with an appropriate hydrogenation catalyst such as palladium on alumina or Raney nickel such as described in
U.S. Patent No. 3,635,841 . - The concentration of the H2O2 oxidant used in the present invention may range generally from about 0.1 wt% to about 100 wt%, preferably from about 1 wt% to about 80 wt%, and more preferably from about 10 wt% to about 60 wt%.
- In one embodiment, an optional solvent may be used in the process of the present invention. The optional solvent useful in the process of the present invention may include for example any inert organic solvent that is inert to H2O2 under the reaction conditions. For example, the solvent may include halogenated alkanes such as dichloromethane; aromatics such as toluene; polar organic solvents such as dimethyl formamide, or ethers such as tetrahydrofuran; alcohols such as t-amyl alcohol and methanol; or fluorinated alcohols such as trifluoroethanol; or mixtures thereof.
- The concentration of the solvent used in the present invention may be in the range of generally from about 1 wt% to about 99 wt%, preferably from about 5 wt% to about 95 wt%, and more preferably from about 10 wt% to about 90 wt%.
- The catalyst useful in the process of the present invention may include for example metal oxides such as alkyltrioxorhenium compounds; heteropolyacids such as phosphotungstate compounds; macroporous and mesomorphous zeolites such as titanium silicate compounds; and transition metal complexes of porphrins, phthalocyanines, and Schiff bases, pyridine and ring annulated pyridine derivatives with at least one or more additional coordinating groups; cyclam; cylen; 8-hydroxyquinoline derivatives; and mixtures thereof, wherein the transition metal may be include for example iron, cobalt, manganese.
- In one embodiment, the catalyst of the present invention is methyltrioxorhenium.
- In another embodiment, the catalyst of the present invention is in-situ generated or isolated ammonium salts of peroxophosphotungstic acid. These salts can be prepared from tungstic acid or phosphotungstic acid and hydrogen peroxide and ammonium salts. The ammonium salts are detailed below under other/optional components.
- In another embodiment, the catalyst of the present invention may be selected from one or more titanium silicate compounds such as TS-1, MCM-41, ZSM-5 or SBA-1. Different transition metals such as Ti, V, Fe, Pd, Nb, Mn, Mo and Cr could be built into the silica frame work to reduce side reactions.
- In another embodiment, the catalyst of the present invention is a transition metal complex. The transition metal for the catalyst is selected from the group comprising of iron, manganese, cobalt, vanadium, chromium, copper and mixtures thereof. The chelants may be cyclen, triazanonane, cyclam or their N-alkyl substituted derivatives. The chelants also may be Schiff bases originating from salicylic aldehyde (or alkyl, aryl substituted analogs) and diamines such as ethylene diamine, o-phenylene diamine, 1, 2-cyclohexyl diamine. Other variants for chelants are phtalocyanine or porphirin and their halogen and alkyl or aryl substituted analogs. The chelants could also be pyridine and ring annulated pyridine derivatives with at least one or more additional coordinating groups on any of the rings. The coordinating groups are selected from hydroxyl groups, thiols, carboxylic acid groups or iminium group in which the carbon can be substituted with alkyl, aryl, O-alkyl, O-aryl, N-alkyl, N-aryl, S-alkyl, or S-aryl groups and imine nitrogen can be substituted with alkyl or aryl groups. For example, the chelants with the pyridine and ring annulated pyridine based structures are depicted below, where R1 are carboxylic acid groups, R2 and R3 could be alkyl, aryl, or O-alkyl, O-aryl, N-alkyl, N-aryl, S-alky or S-aryl groups and R2 and R3 could also be part of a ring system. R4 is situated at any ring position of the annulated ring system and selected from halogens, hydroxyl, thiol, alkyl or aryl groups.
- Preferred transition metal complex catalysts of the present invention are iron(III) chloride- 2,6-pyridine dicarboxylic acid complex modified with either diisopropylamine or benzylamine and manganese(III) 8-hydroxyquinoline complex and its 5,7-substituted analogs; and mixtures thereof.
- There are numerous transition metal complexes of porphrins, phthalocyanines, and Schiff bases, pyridine carboxylates, 8-hydroxy-quinoline, cyclam, cylen, N, N',N"-triazacyclononane which have been used for the epoxidation of styrene and its derivatives as disclosed in Shrinivas et al., Biomimetic Oxidations Using Transition Metal Complexes Encapsulated in Zeolites, Catalysis Surveys from Asia, vol 7, 2-3, 121-131, 2003. In another embodiment of the present invention, the catalysts described in the above reference may be useful for the epoxidation of DVB and result in high yields and epoxide selectivity. The particular selection of the catalyst depends to some extent on the reaction conditions, since DVB polymerizes much easier than styrene and is more sensitive to acidic and basic conditions. Other catalysts described in the art that may be useful in the present invention include a rhenium based catalyst as disclosed in S. Yamakazi, Org. Biomol. Chem., 2007, 5, 2109; an Fe complex catalyst as disclosed in Anilkumar et al., An Efficient Biomimetic Fe-catalyzed Epoxidation of Olefins Using Hydrogen Peroxide, Chem. Commun., 289-291, (2007).al.; and a manganese salophen catalyzed epoxidation as disclosed in Liu et al., A Simple and Versatile Method for Alkene Epoxidation Using Aqueous Hydrogen Peroxide and Manganese Salophen Catalysts, Tetrahedron Lett., 47, 1923, 2006.
- The concentration of the catalyst used in the present invention may range generally from about 0.001 wt% to about 5 wt%, preferably from about 0.01 wt% to about 1 wt%, and more preferably from about .0.1 wt% to about 0.5 wt%.
- The organic modifier used in the process of the present
invention may include for example Lewis bases such as N-containing compounds; either alicyclic amines such as triethyl amine, ethylene diamine, benzyl amine or diisopropyl amine, or heterocyclic amines like pyrazole, pyridine, bipyridine, N,N-dimethylaminopyridine, diazobicyclooctane (DABCO) and their derivatives; N-oxides, alkyl or cyano-substituted analogs; and mixtures thereof. - The organic modifier may depend on the catalyst used in the process of the present invention. For example, when an alkyltrioxorhenium catalyst is used, the organic modifier may include a tertiary amine such as a pyridine or a pyrazole. The amines may be alkyl or aryl substituted at any ring position.
- When a phosphotungstate catalyst is used in the present invention, the organic modifier may be a tertiary amine, ammonium salt, or a quaternary ammonium salt such as methyl-trioctylamine hydrogen sulfate, ammonium salts containing methyl or benzyl groups and long aliphatic hydrocarbon chains (C10-C18), tricaprylammonium chloride, tributylhexadecylammonium bromide, benzalkonium chloride; and mixtures thereof.
- When a manganese porphyrin catalyst is used in the present invention, the organic modifier may be a carboxylic acid, an ammonium carboxylate, or a carboxylic acid anhydride; and mixtures thereof.
- When an iron porphyrin catalyst is used in the present invention, the organic modifier may be for example an aliphatic amine or an imidazole.
- When Schiff bases or pyridine carboxylates or hydroxyquinolines are used additional Lewis bases or, N-heterocycles can be used for example pyrazole and pyrrolidine or carboxylate salts such as ammonium acetate or acetic acid; and mixtures thereof.
- The concentration of the organic modifier used in the present invention may range generally from about 0.01 wt% to about 30 wt%, preferably from about 0.1 wt% to about 20 wt%, and more preferably from about 1 wt% to about 10 wt%.
- In another embodiment of the present invention, the organic modifier may be added to the composition of the present invention to assist in the reaction process; and subsequently, the organic modifier may be removed, if desired, after its use. For example, after the reaction step, the resulting divinylarene dioxide reaction product is isolated and the concentration of the organic modifier in the reaction product is reduced to about 5 weight percent or less; and preferably the concentration of the organic modifier is reduced to about 0.5 weight percent or less. In one embodiment the concentration of the organic modifier is from about 0.004 weight percent to about 5 weight percent; more preferably the concentration of the organic modifier is from about 0.01 weight percent to about 5 weight percent; and most preferably the concentration of the organic modifier is from about 0.5 weight percent to about 1.5 weight percent.
- An assortment of optional additives may be added to the composition of the present invention including for example, other resins, stabilizers, fillers, plasticizers, catalyst de-activators; and mixtures thereof.
- The concentration of the optional additives used in the present invention may range generally from 0 wt% to about 99.9 wt%, preferably from about 0.1 wt% to about 99.9 wt%, more preferably from about 1 wt% to about 99 wt%, and most preferably from about 2 wt% to about 98 wt%. In another embodiment the additives may be from about 0.01 wt % to about 99.9 wt %.
- The preparation of divinylarene dioxides using H2O2 without co-production of undesirable by-products may be achieved by (i) adding to a reactor the following reactants: a divinylarene, a catalyst, an organic modifier, and optionally an inert organic solvent; (ii) contacting the reactants with H2O2; and then allowing the reactant components to react under reaction conditions to produce the corresponding divinylarene dioxide.
- The reaction of the divinylarene with the H2O2 is carried out with an excess of or an equivalent moles of H2O2. Generally, the reaction is carried out at a H2O2:divinylarene mole ratio of at least 2 or more; preferably, from about 2 to about 50; more preferably, from about 2 to about 10; and most preferably, from about 2 to about 4 mole ratio. If less than two moles of H2O2 per mole of divinylarene is used, there would not be sufficient amount of oxidizing agent to epoxidize both of the double bonds in the divinylarene. For example, using one mol H2O2 could provide a product that contains one epoxide group and one double bond on average. In addition, if less than 2 mol H2O2 per mole of divinylarene is used, the resulting reaction product may be unstable, i.e., the product may have an increase in viscosity, and ultimately may gel prior to reaction with an epoxy curing agent. If above 50 moles of H2O2 per mole of divinylarene is used, the benefits of using the H2O2 oxidant in the reaction may no longer be economical; and use of more H2O2 oxidant may be wasteful.
- The reaction conditions include carrying out the reaction under a temperature, generally in the range of from about 0 °C to about 100 °C, preferably from about 5°C to about 80°C, and more preferably from about 20 °C to about 60 °C.
- The pressure of the reaction may be generally from about 0.1 atmosphere (atm) to about 10 atm.
- The reaction process of the present invention may be a batch or a continuous process. The reactor used in the process may be any reactor and ancillary equipment well known to those skilled in the art.
- During the reaction for the preparation of divinylarene dioxides, water is co-produced. The use of H2O2 as the oxidant forms water as the only oxidant by-product. Undesirable by-products from solvents, oxidants, or modifiers such as acetamide and acetic acid are not formed to any substantial degree in the reaction of the present invention as found in the prior art processes. Other undesirable oxidized by-products and derivatives, such as for example carbonyl compounds and hydrolyzed epoxy products, are also not formed in any appreciable quantities using the process of the present invention.
- In the process of the present invention, the insubstantial quantities of the undesirable by-products produced in the reaction of the present invention, are generally, less than about 20 wt % of undesirable by-products; preferably, less than about 10 wt %,; more preferably, less than about 5 wt %; and most preferably zero wt % undesirable by-products.
- After the reaction of the present invention, the co-produced water; and any remaining organic modifier, catalyst, and solvent, may be removed to recover a usable divinylarene dioxide product. Then the product may optionally be purified by well-known means in the art such as by distillation, crystallization.
- One advantage of the present invention process is that high yields of divinylarene dioxides may be produced by the process of the present invention. With high yields of divinylarene dioxides produced, the process of the present invention advantageously requires less recycle and produces less waste.
- The "high yield" of the divinylarene dioxides produced by the process of the present invention, is generally greater than about 30 %; and preferably, ranges from about 70 % to about 100 %; more preferably, from about 80 % to about 100 %; and most preferably, from about 90 % to about 100 % based on divinylarene starting material.
- The divinylarene dioxides prepared by the process of the present invention, particularly those derived from divinylbenzene such as for example divinylbenzene dioxide (DVBDO), are class of diepoxides which have a relatively low liquid viscosity but a higher rigidity than conventional epoxy resins.
- The divinylarene dioxide prepared by the process of the present invention may comprise, for example, any substituted or unsubstituted arene nucleus bearing two vinyl oxide(epoxide) groups in any ring position. The arene portion of the divinylarene dioxide may consist of benzene, substituted benzenes, or (substituted) ring-annulated benzenes or homologously bonded (substituted) benzenes, or mixtures thereof. The divinylbenzene portion of the divinylarene dioxide may be ortho, meta, or para isomers or any mixture thereof. Additional substituents may consist of H2O2-resistant groups including saturated alkyl, aryl, halogen, nitro, isocyanate, or RO- (where R may be a saturated alkyl or aryl). Ring-annulated benzenes may consist of naphthlalene, tetrahydronaphthalene. Homologously bonded (substituted) benzenes may consist of biphenyl, diphenylether.
-
- In the above Structures I, II, III and IV of the divinylarene dioxide product of the present invention, each R1, R2, R3 and R4 individually may be hydrogen, an alkyl, cycloalkyl, an aryl or an aralkyl group; or a H2O2-resistant group including for example a halogen, a nitro, an isocyanate, or an RO group, wherein R may be an alkyl, aryl or aralkyl; x may be an integer of 0 to 4; y may be an integer greater than or equal to 2; x+y may be an integer less than or equal to 6; z may be an integer of 0 to 6; and z+y may be an integer less than or equal to 8; and Ar is an arene fragment including for example, 1,3-phenylene group.
- The divinylarene dioxide product produced by the process of the present invention may include for example alkyl-vinyl-arene monoxides depending on the presence of alkylvinylarene in the starting material.
- In one embodiment of the present invention, the divinylarene dioxide produced by the process of the present invention may include for example divinylbenzene dioxide, divinylnaphthalene dioxide, divinylbiphenyl dioxide, divinyldiphenylether dioxide, and mixtures thereof.
-
-
- When DVBDO is prepared by the process of the present invention, it is possible to obtain one of three possible isomers: ortho, meta, and para. Accordingly, the present invention includes a DVBDO illustrated by any one of the above Structures individually or as a mixture thereof. Structures V and VI above show the meta (1, 3-DVBDO) and para (1,4-DVDBO) isomers of DVBDO, respectively. The ortho isomer is rare; and usually a mixture of DVBDO is mostly produced as an about 2:1 ratio of meta (Structure V) to para (Structure VI). Thus, the present invention preferably includes as one embodiment an about 2:1 ratio of Structure V to Structure VI.
- In one embodiment, the process of the present invention is particularly suited for the preparation of divinylbenzene dioxide, a low viscosity liquid epoxy resin. The viscosity of the divinylarene dioxides produced by the process of the present invention ranges generally from about 10 mPa-s to about 100 mPa-s; preferably, from about 10 mPa-s to about 50 mPa-s; and more preferably, from about 10 mPa-s to about 25 mPa-s at 25 °C.
- The utility of the divinylarene dioxides of the present invention requires their thermal stability to allow their formulation or processing at moderate temperatures (for example, at from about 100 °C to about 200 °C) for up to several hours (for example, for at least 2 hours) without oligomerization or homopolymerization. Oligomerization or homopolymerization during formulation or processing is evident by a substantial increase in viscosity or gelling (crosslinking). The divinylarene dioxides of the present invention have sufficient thermal stability such that they do not experience a substantial increase in viscosity or gelling during formulation or processing at moderate temperatures.
- The following examples and comparative examples further illustrate embodiments of the present invention in detail.
- Various terms and designations used in the following examples are explained as follows: "DVB" stands for divinylbenzene; "DVBO" stands for divinylbenzeneoxide; "DVBDO" stands for divinylbenzene dioxide; "EVB" stands for ethylvinylbenzene; "3-MP" stands for 3-methyl pyrazole; "MTO" stands for methyltrioxorhenium; "HQ" stands for 8-hydroxyquinoline; Aliquat 336 (tricaprylmethyl ammonium chloride) is commercially available from Sigma-Aldrich.
- The product mixtures prepared in the Examples which follow were analyzed by standard gas chromatography (GC) analytical equipment and methods.
- DVB (1 g, 7.68 mmol, 80 % DVB, 20 % EVB), 3-MP (0.126 g, 1.54 mmol) and MTO (19.1 mg, 7.68x10-2 mmol) were dissolved in 10 mL dichloromethane and vigorously stirred in a three-neck flask equipped with a condenser, thermometer and an addition funnel. Hydrogen peroxide (31%, 3.370 g, 30.7 mmol) was added drop wise in the course of 15 minutes and the temperature was kept around 25 °C by cooling the flask in a water bath. The reaction mixture was vigorously stirred and further incubated at 25 °C. The progress of the reaction was monitored by gas chromatography. After 8 hours no more starting material and mono-epoxidized DVB were present.
- The resulting aqueous and organic phases were separated. The organic phase was washed with sodium thiosulfate solution (0.25 M) followed by washing with phosphoric acid (1M) and water. Disregarding the EVB content in the starting material, the desired product, DVBDO, was isolated in 70 % yield.
- The heat stability of DVBDO was assessed by incubating the product at 140 °C and observing if viscosity increase/polymerization occurred. Table I below summarizes how 3-MP concentration in the product affected heat stability.
Table I 3-MP concentration (wt %) Incubation time (hours) Observations 5 0.5 Sample solidified (crosslinked) 1.7 1 Significant viscosity increase 0.5 2 No viscosity increase - Phosphotungstic acid (H3{PO4(WO3)12}, 0.1 g, 0.03 mmol) was dissolved in water (1 mL). Phosphoric acid (30%, 0.022 g, 0.07 mmol) was added, followed by H2O2 (29%, 0.102 g 0.9 mmol). The reaction mixture was stirred at 20 °C for 30 minutes when Aliquat 336 (0.126 g, 0.3 mmol) was added in dichloroethane solution (5 mL). The reaction mixture was stirred at 20 °C for 20 minutes. Then DVB (1 g, 8 mmol, 80 % DVB, 20 % EVB) in dichloroethane solution (5 mL) was added and the temperature was raised to 50 °C. H2O2 (29%, 3.6 g, 32 mmol) was added to the mixture dropwise. The reaction mixture was stirred at this temperature for 6 hours. The reaction mixture was worked up as described in Example 1. A resultant DVBDO product was formed in 20% yield.
- FeCl3 hexahydrate (0.025 mmol) and 2,6-pyridine dicarboxylic acid (0.025 mmol) were mixed in t-amyl alcohol (9 mL) in each of four 20 mL vials equipped with a magnetic stirbar. After stirring 15 minutes, diisopropylamine (3.5 µL, 7.0 µL and 10.5 µL; 0.025, 0.05 and 0.75 mmol, respectively) were added to three separate vials. One vial had no additional amine added to act as a control. To each of the four vials was also added dodecane (57 µL, 0.25 mmol) as an internal standard. The resulting solutions were allowed to stir an additional 30 minutes. Then 95% DVB (71.1 µL, 0.5 mmol) was added to each of the reaction vials. This was followed by rapid addition of 30% H2O2 (228 µL, 2 mmol). The resulting reaction mixtures were allowed to stir at ambient temperature, no attempt being made to control any exotherm which occurred upon addition. At 45 minutes and again at 3 hours after addition of the peroxide, samples (0.25 mL) were removed and analyzed by gas chromatography. Except for the control (no amine added) no peroxide remained at the end of the reaction (3 hours) as indicated by peroxide test strips. The samples were analyzed for the following properties described in Table II.
Table II Equiv. iPr2NH Rxn time (minutes) DVB conversion (%) DVBDO selectivity (%) 0 45 8 0 a 1 45 100 77 b 180 100 73 b 2 45 100 71 b 180 100 72 b 3 45 88 30 c a No reaction products of any sort detected.
b 1-3% selectivity for monoepoxide observed.
c 60% selectivity for monoepoxide observed - Mn(III) complexes were prepared by a literature procedure described in (J. of Catalysis, 256, 154, 2008). A general procedure for testing the manganese(III) complexes of HQ and its halogen substituted analogs is given here. DVB (1 mmol, 80 % DVB, 20 % EVB), catalyst (0.04 mmol), additives, and acetone (3 mL) were transferred into a vial. Ammonium acetate (0.1 mmol) and glacial acetic acid (0.2 mmol) either together or separately were used as additives. Into this mixture hydrogen peroxide (30%, 3 mmol) was added in 5 aliquots in the course of 15 minutes. The reaction mixture was stirred at 25 °C for three hours and analyzed by GC. The results are summarized in Table III as follows:
Table III Chelant Additive DVB (area%) DVBO (area%) DVBDO (area%) HQ Ammonium acetate and acetic acid 27 35 18 HQ Acetic acid 17 35 18 5,7-dichloro-HQ Ammonium acetate and acetic acid 18 33 12 5,7-dibromo-HQ Ammonium acetate and acetic acid 22 31 17
Claims (14)
- A process for preparing a divinylarene dioxide comprising:a) reacting a divinylarene with hydrogen peroxide in the presence of a catalyst and an organic modifier to form a divinylarene dioxide; wherein the hydrogen peroxide is present in an excess or an equivalent mole ratio per mole of vinyl group; wherein said organic modifier is a Lewis base, and wherein said divinylarene dioxide is produced at a yield of greater than 30%; andb) isolating the divinylarene dioxide reaction product; and reducing the concentration of said organic modifier in the reaction product to 5 weight percent or less.
- The process of claim 1, wherein the reaction is carried out at a mole ratio of hydrogen peroxide:divinylarene dioxide of at least 2 or more.
- The process of claim 1, wherein hydrogen peroxide is generated in-situ using hydrogen and oxygen; or wherein hydrogen peroxide is generated in-situ using an anthraquinone/tetrahydroanthraquinone process in the presence of a hydrogenation catalyst.
- The process of claim 3, wherein the hydrogenation catalyst is palladium; alumina or Raney nickel; or mixtures thereof.
- The process of claim 1, wherein the catalyst is a titanium dioxide-gold catalyst or a gold catalyst supported on a non-porous and mesoporous titania-silica; or wherein the catalyst comprises metal oxides; or wherein the catalyst comprises transition metal complexes; wherein the catalyst comprises heteropolyacids.
- The process of claim 1, wherein the divinylarene is divinylbenzene; and wherein the divinylarene dioxide formed is divinylbenzene dioxide.
- The process of claim 1 wherein the catalyst comprises methyltrioxorhenium; or wherein the catalyst comprises cobalt or manganese salen complexes; or wherein the catalyst comprises manganese or iron-chelant complexes; or wherein the catalyst comprises iron or manganese porphyrins; or wherein the catalyst comprises phosphotungstic acid ammonium salts.
- The process of claim 7, wherein the chelant of the manganese or iron complexes are pyridine and ring annulated pyridine derivatives with at least one or more additional coordinating groups on any of the rings.
- The process of claim 8, wherein the coordinating groups are hydroxyl or thiol groups, comprising 8-hydroxyquinoline and its substituted analogs; or carboxylic acid groups comprising 2,6-pyridinedicarboxylic acid; or iminium groups in which the carbon can be substituted with alkyl,aryl or O-alkyl, O-aryl, N-alkyl, N-aryl, S-alkyl or S-aryl groups and imine nitrogen can be substituted with alkyl or aryl groups.
- The process of claim 7 including salen chelants originating from alkyl, aryl, o-alkyl, O-aryl or halogen substituted salicylic aldehyde and diamines comprising ethylene diamine, 1,2 cyclohexyl diamine and 1,2-phenylenediamine and their alkyl,aryl or halogen substituted analogs.
- The process of claim 7, wherein the ammonium ion comprises tetrabutyl ammonium salts; or ammonium salts with one or two long alkyl chains having longer than C8 chains; and methyl and/or benzyl or cetylpyridinium groups; and mixtures thereof.
- The process of claim 7, wherein the catalyst is immobilized on a solid support; wherein the solid support comprises zeolites, clays, silica, alumina, or polymers; or wherein the polymer solid support comprises polyglycerol, polystyrene, polymethacrylates, dendrimers, or polyvinyl-pyridine.
- The process of claim 1, wherein the concentration of said catalyst ranges from 0.001 weight percent to 5 weight percent; wherein the concentration of said divinylarene ranges from 1 weight percent to 100 weight percent; and wherein the hydrogen peroxide concentration ranges from 0.1 weight percent to 100 weight percent.
- The process of claim 1 including a solvent; wherein the solvent comprises chlorinated hydrocarbons; aromatic hydrocarbons; polar solvents; ethers; alcohols or fluorinated alcohols; or mixtures thereof.
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US14145708P | 2008-12-30 | 2008-12-30 | |
PCT/US2009/065435 WO2010077483A1 (en) | 2008-12-30 | 2009-11-23 | Process for preparing divinylarene dioxides |
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EP2325876A3 (en) | 2009-11-23 | 2016-04-20 | DOW Global Technologies | Epoxy resin formulations for underfill applications |
BR112012010342A2 (en) | 2009-11-23 | 2019-09-24 | Dow Global Technologies Llc | stiffened epoxy resin formulation and stiffened epoxy resin article |
KR20120114295A (en) * | 2009-12-09 | 2012-10-16 | 다우 글로벌 테크놀로지스 엘엘씨 | Epoxy resin compositions |
KR20120104590A (en) * | 2009-12-09 | 2012-09-21 | 다우 글로벌 테크놀로지스 엘엘씨 | Divinylarene dioxide presins |
US20110315916A1 (en) | 2010-06-29 | 2011-12-29 | Dow Global Technologies Inc. | Curable composition |
CN102757408B (en) * | 2011-04-29 | 2014-08-20 | 中国石油化工股份有限公司 | Method for oxidizing chloropropene |
EP2707412B1 (en) | 2011-05-13 | 2016-01-06 | Dow Global Technologies LLC | Insulation formulations |
JP6030125B2 (en) | 2011-05-13 | 2016-11-24 | ダウ グローバル テクノロジーズ エルエルシー | Insulation compound |
JP6162698B2 (en) | 2011-08-18 | 2017-07-12 | ブルー キューブ アイピー エルエルシー | Curable resin composition |
JP2014524468A (en) * | 2011-08-22 | 2014-09-22 | ダウ グローバル テクノロジーズ エルエルシー | Cyclic carbonate monomers and polymers prepared therefrom |
WO2013043363A2 (en) | 2011-09-21 | 2013-03-28 | Dow Global Technologies Llc | Epoxy-functional resin compositions |
EP2776412B1 (en) | 2011-11-08 | 2017-05-03 | Blue Cube IP LLC | Process for preparing a divinylarene dioxide |
US20140256909A1 (en) | 2011-11-08 | 2014-09-11 | Dow Global Technologies Llc | Curable compositions |
BR112015007956A2 (en) | 2012-10-17 | 2017-07-04 | Dow Global Technologies Llc | composition, process for preparing a composition, prepreg, coating, composite, electrical laminate and electronic adhesive |
US20150247031A1 (en) | 2012-10-19 | 2015-09-03 | Dow Global Technologies Llc | Polymer particle dispersions with divinylarene dioxides |
TW201429963A (en) | 2012-10-26 | 2014-08-01 | Dow Global Technologies Llc | Novel epoxide compound |
CN103570617B (en) * | 2013-11-15 | 2016-05-04 | 浙江荣凯科技发展股份有限公司 | A kind of preparation method of 3-cyano group-pyridine N-oxides |
JP2017501288A (en) | 2013-11-26 | 2017-01-12 | ダウ グローバル テクノロジーズ エルエルシー | Curing agent composition |
CN105793333A (en) | 2013-12-18 | 2016-07-20 | 陶氏环球技术有限责任公司 | Curable compositions |
WO2015123092A1 (en) | 2014-02-11 | 2015-08-20 | Northwestern University | Epoxidation process |
US9943839B2 (en) | 2014-07-15 | 2018-04-17 | Northwestern University | Catalyst composition and process for preparing olefin oxides |
WO2016099829A1 (en) | 2014-12-15 | 2016-06-23 | Dow Global Technologies Llc | Process for producing a composite article |
AU2015371229B2 (en) | 2014-12-23 | 2019-09-12 | Dow Global Technologies Llc | Treated porous material |
WO2016160346A1 (en) | 2015-03-20 | 2016-10-06 | Blue Cube Ip Llc | Curable compositions |
JP7160532B2 (en) | 2015-03-20 | 2022-10-25 | ブルー キューブ アイピー エルエルシー | Curable composition |
CN106084095A (en) * | 2016-06-13 | 2016-11-09 | 张玲 | A kind of adsorbing material of purifying lithium |
CN108047168B (en) * | 2017-12-20 | 2021-02-26 | 东南大学 | Synthesis method of epoxy glycidyl oleate |
CN109232414A (en) * | 2018-10-25 | 2019-01-18 | 老河口市天和科技有限公司 | The preparation method of N- oxo niacinamide |
CN113004135A (en) * | 2021-03-03 | 2021-06-22 | 南京林业大学 | Method for preparing thujopsis japonica ketonic acid by utilizing MTO catalysis |
CN116496235B (en) * | 2023-06-26 | 2023-09-19 | 络合高新材料(上海)有限公司 | Method for preparing vinylarene epoxide through photocatalysis synergistic oxidation reaction |
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US3635841A (en) | 1969-06-16 | 1972-01-18 | Engelhard Min & Chem | Novel anthraquinone hydrogenation catalyst |
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US5463090A (en) * | 1994-10-27 | 1995-10-31 | Arco Chemical Technology, L.P. | Integrated process for epoxide production |
US5578740A (en) * | 1994-12-23 | 1996-11-26 | The Dow Chemical Company | Process for preparation of epoxy compounds essentially free of organic halides |
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